THE  DETERMINATION  OF  SULPHUR  IN  OIL 


BY 


FREDERICK  EWART  VANDAVEER 


THESIS 


FOR  THE 

DEGREE  OF  BACHELOR  OF  SCIENCE 
IN  CHEMISTRY 


COLLEGE  OF  LIBERAL  ARTS  AND  SCIENCES 
UNIVERSITY  OF  ILLINOIS 
1922 


1922 

Y28I 


UNIVERSITY  OF  ILLINOIS 


■■I' 


I ' January.. .21, 191SS. 

' 

I ' 

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THIS  IS  TO  CERTIFY  THAT  THE  THESIS  PREPARED  UNDER  MY  SUPERVISION  BY 

...|^r.e.d.er.iclc-Swart...YancLaY.e.er 

ENTITLED .....T.he...Deter.mina,tian...af  ...Sulphur....in...Oil- 


IS  APPROVED  BY  ME  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR  THE 
DEGREE  OF Bac.h«lor...o.f...Scienc.e. 


Instructor  in  Charge 


Approved  : 


HEAD  OF  DEPARTMENT  OF 


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TABLE  OF  CONTENTS 


Page 

Aclmowle  dgement 

I  Introduction  1-8 

1 . Purpo  8e  1 

2.  Nature  of  the  Problem  1-2 

3.  Historical  2-6 

4.  Criticisms  "^-8 

II  Experimental  9-18 

1.  Work  on  Method  of  Parr-Whittum  9-13 

2.  New  Methods  Tried.  13-15 

3.  Work  on  the  Rothe  Method  16-18 

III  Results  and  Discussion  19-25 

IV  Summary  and  Conclusions  26-27 

V  Bibliography  28 


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ACOOWLEDGSMEUT 

I wish  to  take  this  opportunity  of  thanking 
Professor  S.  W.  Parr  for  the  suggestion  of  this  problem 
and  for  the  friendly  supervision  and  interest  he  has 
given  me  at  all  times.  His  personal  interest  has  meant 
more  to  me  than  any  other  factor  in  this  work.  I also 
wish  to  thank  Pr.  T.  E.  Lajmg  for  his  interest  and  sug- 
gestions, and  Cosden  and  Company  of  Tulsa,  Oklahoma  for 
twelve  of  the  oils  with  which  I worked. 


Digitized  by  the  Internet  Archive 
in  2015 


https://archive.org/details/determinationofsOOvand 


TH3  DETSRMIMTIOIT  OP  SULPUR  IH  OIL 
I.  INTRODUCTION 

1. -  PURPOSE. 

The  purpose  of  this  investigation  has  been  the  study  of  the 
most  suitable  methods  for  the  determination  of  sulfur  in  oils  where 
the  percentage  of  sulfur  is  low. 

2. -  NATURE  OP  THE  PROBLEM 

The  determination  of  sulfur  in  oils  that  have  not  less  than 
.5  percent  of  sulfur  has  been  solved  very  satisfactorily  by  several 
methods,  namely:  (a)  By  use  of  oxygen  bomb^;  (b)  by  fusion  with 

sodium  peroxide^;  (c)  by  the  combustion  method,  using  a stream  of 
pure  oxygen^,  \^nien  these  methods  are  applied  to  oils  with  a very 
low  percentage  of  sulfur,  difficulties  are  encountered.  In  the 
oxygen  bomb,  about  1 gram  is  the  limit,  and  in  the  Parr  peroxide 
bomb,  the  limit  of  the  amount  of  oil  that  can  be  completely  burned 
is  about  .5  of  a gram.  This  amount  of  oil,  if  it  contained  only 
.1  to  .3  percent  of  sulfur,  would  give  a barium  sulfate  precipitate 
weighing  from  .004  to  .0108  gram.  In  order  to  make  the  experimental 
errors  lov^,  a barium  sulfate  precipitate  should  weigh  at  least  .01 
gram,  and  the  determination  is  much  more  accurate  if  the  precipitate 
weighs  .1  gram.  Por  oils  low  in  sulfur,  therefore,  these  two  bomb 
methods  are  not  entirely  satisfactory  even  though  several  combus- 
tions may  be  made  and  added  together  to  give  a good  weighable 
quantity  of  barium  sulfate,  for  the  reason  that  after  three  or 
four  combustions,  the  amount  or  concentration  of  sodium  and  potas- 
sium salts  in  the  case  of  the  peroxide  bomb  would  be  very  great. 


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In  the  case  of  the  oxygen  bomh,  the  time  element  would  he  a factor. 
Another  objection  to  the  use  of  the  oxygen  bomb  is  that  it  is  so 
expensive  that  not  every  oil  laboratory  can  afford  it.  The 
combustion  of  several  grams  of  oil  in  a stream  of  oxygen  would 
also  be  a very  difficult  proposition  and  in  the  case  of  lubrica- 
ting and  heavy  cylinder  oils,  it  would  not  be  at  all  satisfactory 
because  of  the  difficulty  of  controlling  the  combustion  process. 

If  some  oxidizing  agent  is  used  outside  of  a bomb,  it  must 
be  an  exceedingly  strong  one  to  oxidt  ze  all  of  the  sulfur  com- 
pounds in  oil  before  some  of  them  escape.  Sulfur  is  found  in 
oil  in  many  different  forms,  all  of  which  have  not  yet  been  dis- 
covered, possibly.  Then  too,  different  oils  contain  different 
sulfur  compounds.  Although  one  oil  may  contain  the  volatile 
hydrogen  sulfide,  another  might  not  contain  a trace  of  it.  Some 
of  the  knov/n  compounds  that  have  been  found  in  different  oils  are: 
Hydrogen  sulfide^,  carbon  bisulfide^,  alkyl  sulfides  (thio  ethers)^, 
thiophenes'^ , thiophanesQ,  mercaptans^,  free  sulfur^9  organic  sul- 
fonates and  sulfates^^.  To  oxidize  all  of  these  compounds,  a pow- 
erful oxidizing  agent  is  needed. 

Some  method,  therefore,  is  needed  whereby  from  5 to  10  grams 
of  oil  could  be  oxidized  at  once  in  approximately  the  same  time 
that  it  takes  to  make  three  or  four  peroxide  bomb  combustions,  and 
this  is  the  problem  of  this  investigation. 

3.-  HISTORICAL 

A great  number  of  methods  for  the  oxidation  of  sulfur  in  oil 
have  been  proposed, but  many  of  them  are  of  such  slight  difference 
from  the  main  methods  that  they  need  not  be  reviewed.  Most  of  them, 
however,  may  be  classed  under  three  heads. 


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I  Dry  J^sion  Methods. 

(a)  With  alkalis  and  suhseq.uent  oxidation 
with  "bromine.  Heath^^,  Sadtler^^,  Hunde- 
schagen^'^,  Garret  and  Lomax^^,  methods  are 
illustrations. 

(b)  With  a mixture  of  alkalis  and  oxidizing 
agents.  Blair^^,  Peckham^’^,  Lidow^®, 

Aufrecht^^,  Eschka^*^,  are  the  leading 
men  for  this  type  of  fusion. 

(c)  Parr  Peroxide  Bomb?^ 

II  Oxidation  with  wet  Oxidizing  Agents. 

(a)  At  atmospheric  pressures.  Lecocq  and 
"Vandevort^^ , Goetzl^^  , Calvert^"^. 

(b)  At  high  pressure.  Carius^® , Anelli^^, 

Holand27. 

Ill  Burning  Methods. 

(a)  Using  a lamp^®,^^;  Sander s^^ . 

(b)  In  a stream  of  pure  oxygen  in  a combus- 
tion tube.^^ 

(c)  In  pure  oxygen  at  atmospheric  pressure^^. 

(d)  In  an  oxygen  bomb  under  30-40  atmospheres^^. 

The  principle  of  the  dry  fusion  method  under  (a)  is  to  fuse 

the  oil  directly  with  some  alkali  and  complete  the  oxidation  with 
bromine,  precipitating  the  sulfur  in  the  usual  way  as  barium  sulfata 
Heath  and  Sadtler  used  sodium  carbonate  and  magnesium  oxide  as  a 
fusion  mixture;  Hundeschagen  used  sodium  and  potassium  carbonates 
and  magnesium  oxide;  Garret  and  Lomax  used  the  inner  crucible 


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method  with  oalcium  oxide  and  sodium  carbonate . 

The  dry  fusion  method  under  (b)  differs  Tery  little  from  (a). 
Blair,  Pechham  and  Lidow  fuse  the  sample  with  sodium  carbonate  and 
potassium  nitrate.  Aufrecht  fuses  with  acid  sodium  carbonate  and 
ammonium  nitrate.  Eschka  uses  sodium  carbonate,  magnesium  oxide 
and  sometimes  ammonium  nitrate. 

The  best  dry  fusion  method  is  that  of  using  the  Parr  peroxide 
bomb.  Pranks  uses  one  measure  of  sodium  peroxide,  one  gram  of 
potassium  chlorate,  .2  gram  of  benzoic  acid  and  .5  gram  of  oil.  He 
ignites  the  thoroughly  mixed  material  in  the  bomb,  takes  the  product 
(solids)  into  solution  with  water  and  hydrochloric  acid,  and  pre- 
cipitates the  sulfur  as  barium  sulfate. 

Burning  oil  in  a lamp  is  of  course  applicable  only  to  burning 
oils.  The  principle  involved  is  the  burning  of  several  grams  of 
oil,  collecting  all  the  products  of  combustion  in  a solution  that 
would  absorb  all  of  the  sulfur  dioxide  and  trioxide,  with  subsequent 
oxidation  with  bromine  and  precipitation  as  barium  sulfate. 

Burning  the  oil  in  a stream  of  pure  oxygen  in  a combustion 
tube  requires  the  ordinary  organic  combustion  train  with  the  usual 
wash  bottles  at  the  entrance,  and  potash  absorption  bulbs  at  the 
exit.  This  method  requires  a great  deal  of  skill. 

Burning  the  oil  at  atmospheric  pressure  in  pure  oxygen  involves 
the  use  of  a ten  liter  glass  bottle  fitted  with  a dropping  funnel  of 
100  cc.  capacity  filled  with  hydrochloric  acid  and  a little  bromine 
water.  The  oil  is  placed  in  the  bottle  in  a small  crucible  and 
when  the  bottle  is  filled  with  oxygen,  is  ignited  by  an  electric 
current.  The  products  of  combustion  are  taken  up  in  the  usual  way. 


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(5) 


The  Gomhustion  of  oil  in  an  oxygen  homh  is  carried  out  as  fol- 
lows: 0.7  to  1.0  gram  of  oil  is  hurned  in  the  homh  containing 

10  cc.  of  water  and  oxygen  under  a pressure  of  30  atmospheres.  A 
lower  pressure  sometimes  gives  inaccurate  results.  If  the  sample 
contains  more  than  3 percent  sulfur,  the  homh  is  allowed  to  stand 
in  its  water  hath  for  15  minutes  after  ignition.  In  case  the  sul- 
fur content  is  as  high  as  5 percent,  oxygen  under  40  atmospheres  is 
used^^.  The  contents  of  the  homh  are  thoroughly  washed  out  and  the 
solution  treated  for  a gravimetric  determination  of  the  sulfur  as 
harium  sulfate. 

In  the  oxidation  with  wet  oxidizing  agents,  nitric  acid  and 
fuming  nitric  acid  are  hy  far  the  more  common,  although  Lecoccj  and 
Vandevort  oxidize  with  hydrogen  peroxide,  and  Marchlewski^^  uses 
nitric  acid  and  potassium  perchlorate.  G-oetzl  concentrates  the 
sample  to  a small  hulk  with  fuming  nitric  acid,  then  fuses  with 
sodiom  carbonate  and  potassium  nitrate.  Carius  seals  the  oil  with 
fuming  nitric  acid  in  a glass  tube  and  heats  under  pressure  to 
complete  the  oxidation.  Anelli  introduces  harium  nitrate  into  the 
Carius  tube  and  claims  to  get  more  accurate  results.  Sanders^*^,  in 
determining  the  total  sulfur  in  kerosene,  weighs  2 to  3 grams  of  the 

011  into  a 100  cc.  dish,  sprinkles  .01  gram  of  powdered  potassium 
bromide  over  the  surface  and  adds  4 cc.  of  fuming  nitric  acid. 

When  this  reaction  ceases,  the  mixture  is  evaporated  on  a water 
hath  to  a dark  brown  color.  Then  he  adds  .5  gram  of  magnesium 
oxide,  mixes  thoroughly,  dries  over  a sulfur-free  flame  and  heats 
until  the  mass  tends  to  solidify  on  cooling.  This  mixture  is  put 
in  a Parr  peroxide  homh  and  ignited  with  a measure,  approximately 


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(6) 


14  grams,  of  sodium  peroxide. 

38 

’»Yaters  weighs  .5  to  1.5  grams  of  oil  into  a 100  oo.  dish,  adds 
5 GO.  of  concentrated  nitric,  and  saturates  with  bromine  water  and 
digests  on  a steam  bath  for  -g-  hour,  and  then  in  direct  contact  with 
the  steam  for  E to  3 hours.  At  the  end  of  this  time,  he  adds  10  to 
12  grams  of  sodium  carbonate,  drys  this  mixture  and  ignites  it  slow- 
ly. The  resultant  mixture  is  taken  into  solution  and  the  barium  sul- 
fate precipitated. 

Parr- Whit tum^^weigh  5 to  10  grams  of  the  oil  into  an  80  mm. 
dish.  Dust  about  200  mg.  of  powdered  potassium  bromide  over  the 
surface  and  add  4 to  5 cc.  of  fuming  nitric  acid.  After  the  reac- 
tion ceases  in  the  cold,  it  is  heated  on  a steam  bath  until  the 
liquid  becomes  viscous.  Then  add  2 grams  of  Escha  mixture,  mixing 
it  thoroughly  with  the  oil.  The  heat  is  then  increased  until  the 
mixture  catches  fire  and  burns  to  a white  powder.  This  powder  is 
taken  into  solution  and  the  sulfur  precipitated  as  barium  sulfate. 

Rothi'^weighs  3 to  4 grams  of  oil  into  a 250  cc.  (1000  cc)"^^ 
round  bottom  flask,  with  1.5  gram  of  magnesium  oxide  and  30  to  40  cc. 
of  concentrated  nitric  acid.  Hood.  After  the  first  violent  reaction, 
the  flask  is  heated  gently  for  1^  to  2 hours  on  a sand  bath,  while 
the  liquid  is  kept  boiling  gently.  The  excess  nitric  acid  is  then 
evaporated  over  a free  flame  and  the  residue  heated  till  the  ni- 
trates begin  to  decompose.  Oool,  add  10  cc.  concentrated  nitric 
acid  and  heat  15  minutes.  Evaporate  to  dryness,  keeping  the  flask 
in  constant  motion.  Heat  with  a triple  burner  till  all  the  nitrates 

are  decomposed  and  the  residue  is  white.  Take  up  in  concentrated 
hydrochloric  by  heating.  Filter  and  add  barium  chloride. 


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(7) 


4.-  CRITICISMS. 

The  dry  fusion  methods,  with  the  exception  of  the  Parr  peroxide 
bomh,  are  not  very  successful  for  fast  burning  substances  such  as 
oils,  because  oils  volatilize  and  lump  so  rapidly  that  the  fusion 
mixture  does  not  have  a chance  to  retain  all  of  the  sulfur  com- 
pounds. Practically  all  of  these  methods  are  successful  for  coals 
and  similar  substances.  The  peroxide  bomb  is  good  for  coals  and 
oils  with  a sulfur  content  above  .5  percent,  but  with  oils  lower 
than  .5  percent,  several  combustions  would  have  to  be  made  in 
order  to  get  a good  amount  of  barium  sulfate.  This  bomb  is  limited 
to  about  .3  gram  of  oil. 

The  burning  methods  have  several  drawbacks  also.  In  the  lamp 
method,  not  all  oils  could  be  treated  because  many  low  percentage 
sulfur  oils,  such  as  lubricating,  cylinderoils,  etc.,  do  not  burn 
readily.  Another  criticism  is  that  some  sulfur  is  retained  in 
the  wick  and  it  too  must  be  analyzed.  Burning  in  a stream  of  pure 
oxygen  in  a combustion  tube  is  fairly  satisfactory,  but  it  requires 
skill  in  operation  or  the  oil  will  burn  too  rapidly  and  thus  lose 
some  of  the  sulfur  compounds.  It  is  not  a quick  method.  Burning 
in  a large  flask  at  atmospheric  pressure  using  pure  oxygen  is  not 
satisfactory  because  the  manipulation  of  the  apparatus  is  difficult 
and  the  oxidation  is  not  always  dependable.  Burning  in  an  oxygen 
bomb  under  30  to  40  atmospheres  is  a very  good  method  with  no  ob- 
jections except  that  the  apparatus  is  expensive,  and  too  small  a 
sample  of  the  oil  has  to  be  taken,  as  in  the  case  of  the  peroxide 
bomb. 

Oxidation  by  nitric  acid  at  high  pressure,  as  in  the  Oarius 


(8) 

and  Anelli  methods,  is  accurate,  and  enough  oil  can  he  taken  for  a 

good  precipitate  of  barium  sulfate,  but  there  is  great  danger  of 

the  sealed  tube  exploding,  so  it  is  not  reliable.  According  to 

42 

Allen  and  Robertson  , oxidation  by  nitric  acid  at  atmospheric  pres- 
sure is  not  satisfactory  for  oils  and  the  methods  they  have  listed 
are  possibly  not  satisfactory. 

In  this  review  of  the  literature,  therefore,  the  method  of  pro- 
cedure on  oils  having  a low  percentage  sulfur  narrows  down  to  that 
of  Sanders,  Waters,  Rothe,  Parr  and  Whittum.  Sanders  applied  his 
method  only  to  kerosene,  and  is  not  applicable  to  crude  oils,  fuel 
oils,  lubricating  oils,  etc.  He  would  have  difficulty  getting  the 
mixture  from  the  dish  to  the  bomb.  Furthermore,  he  could  only  use 
a rather  low  weight  of  oil.  Waters  only  uses  from  .5  to  1.5  grams 
of  oil,  and  the  ignition  of  the  oil-sodium  carbonate  mixture  pre- 
sents a big  difficulty  in  most  oils,  spattering  and  incomplete  com- 
bustion being  the  main  ones.  Rothe  used  too  small  a flask  at  first, 
but  now  the  modification  in  Vol.  XX  of  A.M.S.T.M.  , using  a liter 
round  bottom  flask,  removes  that  difficulty.  Also  Rothe  used  con- 
centrated nitric  acid  and  burned  down  the  second  time  with  concen- 
trated nitric  acid,  thus  making  the  method  a rather  long  one.  This 
work  was  undertaken  with  the  idea  of  starting  with  from  5 to  10 
grams  of  oil  and  making  one  combustion  so  that  any  oil,  no  matter 
how  low  the  percentage,  could  be  determined.  After  studying  the 
different  methods,  the  work  narrowed  dovm  to  a study  of  Sanders'' 
Waters',  Rothefe  and  Parr  and  Y{hittum' s work,  the  object  being  to  see 
which  one  was  the  best,  and,  if  possible,  improve  on  them. 


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i/  , aiT'tc^? . 0 ‘ ‘tut  t 


(9) 


II.  EZPSRBI31JTAL 

1.-  WORK  ON  PARR-YfHITTUM  METHOD. 

The  method  as  stated  in  the  historical  part  of  this  paper  was 
as  follows:  Weigh  5 to  10  grams  of  the  oil  into  an  80  mm.  porce- 

lain dish.  Dust  20  mg.  of  finely  powdered  potassiiun  bromide  over 
the  surface.  Add  4 to  5 cc.  of  pure  fuming  nitric  acid,  drop  by 
drop,  with  constant  stirring.  (This  reaction  is  usually  very  vig- 
orous, and  care  must  be  taken  to  prevent  loss  by  spattering. ) 

After  the  reaction  has  ceased,  place  the  dish  on  a steam  bath  and 
evaporate  the  liquid  until  it  becomes  viscous.  Add  about  2 grams 
of  Eschka  mixture  (2  parts  magnesium  oxide,  1 part  sodium  carbonate) 
and  mix  thoroughly  with  the  oil,  being  careful  to  take  up  all  the 
oil  that  may  adhere  to  the  sides  of  the  dish.  Place  the  dish  over 
an  alcohol  flame  and  allow  the  mixture  to  dry  slowly.  The  heat 
should  be  increased  gradually  until  the  mixture  catches  fire  and 
burns  to  a white  powder,  breaking  up  the  large  particles  occasion- 
ally with  a glass  rod.  (This  burning  should  be  done  under  the  hood) 
After  cooling,  brush  the  powder  into  a beaker  containing  50  cc.  of 
water  and  add  hydrochloric  acid  until  the  solution  is  acid.  Heat 
and  filter.  The  filtrate  is  then  prepared  for  the  gravimetric  bari- 
um sulfate  precipitation. 

The  first  determinations  were  run  on  a fuel  oil  used  here  in 
the  oil  furnaces.  Ho  difficulties  were  encountered  in  going  through 
the  determination  until  the  Eschka  mixture  was  added.  It  was  very 
difficult  to  get  a good  mixture  v/ith  the  viscous  oil,  and  on  igni- 
tion a great  deal  of  loss  by  spattering  took  place.  Furthermore, 
it  was  impossible  to  burn  off  all  of  the  carbonaceous  material  to  a 


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(10) 


white  powder.  After  trying  several  ignitions,  it  was  finally  de- 
cided that  possibly  water  in  the  oil  mixture  from  the  steam  hath 
might  he  the  cause  of  the  spattering,  and  so  several  determinations 
were  run,  Iceeping  everything  as  dry  as  possible,  heating  the  mixture 
over  a very  low  Bunsen  flame  and  protecting  the  dish  from  the  sulfur 
of  the  gas  flame  by  a large  asbestos  sheet  with  a hole  cut  in  the 
bottom  just  large  enough  for  the  dish  to  rest  its  weight  in  the  wire 
gauze  beneath.  Before  the  oil  became  too  viscous,  enough  sodiiun 
carbonate  for  good  mixing  (approximately  10  grams)  was  added  and 
thoroughly  mixed,  then  the  magnesium  oxide  was  added  for  air  pene- 
trability. This  mixture  was  thoroughly  dried  over  the  Bunsen  flame 
and  then  ignited  slowly  by  raising  the  temperature.  As  a result, 
there  was  no  loss  by  spattering.  But  in  all  of  the  experiments  per- 
formed, it  was  never  possible  to  burn  off  all  of  the  carbon.  The 
addition  of  alcohol  did  not  aid  the  burning  off  of  the  carbon. 

There  was  always  from  .1  to  .6  gram  of  carbon  left  on  the  filter 
paper  after  the  residue  was  dissolved  in  water  and  hydrochloric  acid. 
Upon  analysis  of  this  black  residue  in  the  peroxide  bomb,  there  was 
never  more  than  a trace  of  barium  sulfate  found,  - no  more  than 
would  be  expected  from  an  analysis  of  the  reagents,  with  possibly 
a little  sulfur  from  the  carbon  that  had  not  been  thoroughly  washed 
out . 

Having  worked  out  the  mechanics  of  the  determination,  the  ques- 
tion arose  as  to  how  much  potassium  bromide,  if  any  at  all,  should 
be  used  and  whether  potassium  bromide  was  better  than  bromine  water 
as  an  aid  to  oxidation.  It  was  found  that  potassium  bromide  and 
bromine  were  an  aid  to  oxidation,  that  from  .E  to  .5  gram  of  potas 
^7Tn  bromide  was  sufficient  and  that  it  did  not  matter  what  fraction 


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in  between  or  above  was  used.  Amounts  down  to  .01  were  tried  and 
it  was  found  that  even  that  much  aided  oxidation.  It  was  found 
more  convenient,  however,  to  use  amounts  between  .2  and  ^ gram. 
Liquid  bromine  and  potassium  bromide  have  about  an  equal  effect, 
as  the  data  will  show,  so  there  is  no  preference  except  that 

toward 

by  adding  bromine  water,  some  water  is  added  to  the  oil  and  helps 
causirg  it  to  spatter.  In  this  work,  potassium  bromide  was  used  for 
that  reason.  The  data  is  given  in  Table  I regarding  this  part  of 
the  work.  Otsubo's  thesis^^  also  bears  this  work  out. 

In  some  of  the  later  work  from  4 to  10  cc.  of  fuming  nitric 
acid  was  used  to  be  sure  of  complete  oxidation.  Ho  check,  however, 
was  run  against  the  smaller  amounts.  It  was  also  found  advisable 
to  use  a larger  porcelain  dish,  because  of  better  air  penetrability. 

The  method  in  all  the  later  work  was  as  follows:  Weigh  5 to 
10  grams  of  the  oil  into  a 110  ram.  or  150  mm.  porcelain  dish.  Dust 
from  .2  to  .5  gram  of  finely  powdered  potassium  bromide  over  the 
surface.  Add  4 to  10  cc.  of  fuming  nitric  acid  slowly  v/ith  stir- 
ring, and  allow  the  mixture  to  stand  for  about  15  minutes.  Then 
heat  over  a very  low  Bunsen  flame  (with  the  asbestos  protection) 
until  the  oil  becomes  rather  viscous  ) experience  is  necessary  to 
know  about  the  right  jMDint  to  stop  heating)  Then  add  enough  sodium 
carbonate  (approximately  10  grams)  to  take  up  all  the  oil  and  make 
a sort  of  powder.  If  the  oil  has  become  too  viscous,  this  cannot 
be  done  because  it  will  ball  up  instead  of  mixing.  Vsfhen  the  sodium 
carbonate  has  been  thoroughly  incorporated,  a gram  or  two  of  magnes- 
ium oxide  is  added  to  give  a fluffy  mixture  and  insure  a better  ig- 
nition. Then  dry  this  mixture  over  the  Bunsen  flame.  When  it  is 
dry,  gradually  raise  the  temperature.  White  fumes  come  off  slowly 


(12) 

and  if  the  temperature  is  raised  too  fast,  there  is  a point  v/here  a 
rather  violent  action  sets  in  with  considerable  evolution  of  white 
fumes.  But  there  is  no  loss  by  spattering,  and  checlcs  against  the 
peroxide  bomb  show  no  loss  of  sulfur.  Continue  heating  over  a full 
Bunsen  flame  until  as  much  of  the  carbon  as  possible  is  driven  off. 
(There  is  always  some  left)  This  tahes  about  an  hour.  The  residue, 
partly  white  and  partly  black,  is  taken  into  solution  with  water 
and  hydrochloric  acid,  filtered,  and  the  filtrate  prepared  for  the 
usual  barium  sulfate  precipitation.  Data  is  given  in  Table  III. 

In  this  method  there  are  two  or  three  places  where  one  might 
suspect  that  sulfur  is  lost.  In  the  first  place,  it  might  be  lost 
by  volatilization  before  the  fuming  nitric  acid  had  a chance  to 
oxidize  it  and  so  in  order  to  prevent  this,  the  fuming  acid  was  put 
on  the  oil  as  soon  as  possible  after  it  was  put  in  the  dish.  Even 
then,  it  would  hardly  be  possible  in  the  case  of  kerosene,  gasoline, 
and  naptha,  to  prevent  some  volatilization.  But  for  heavy  oils, 
such  as  lubricating  oil  and  cylinder  oil,  it  is  all  right  and  no 
loss  occurs.  Another  place  where  one  might  think  some  loss  occurred 
is  in  the  ignition  when  a rapid  evolution  of  gas  takes  place,  but  it 
is  proven  by  checks  against  another  method  that  there  is  none.  The 
whole  method  depends  upon  the  complete  oxidation  by  the  fuming  nitric 
and  potassium  bromide  and  the  fixation  as  sodium  or  magnesium  sul- 
fate before  this  big  evolution  occurs.  Otherwise,  v/e  would  lose 
some  sulfur.  One  might  look  with  suspicion  on  the  fairly  large 
amount  of  carbon  left  after  ignition  and  also  upon  the  black  carbon- 
aceous material  that  is  so  hard  to  get  off  the  dish.  But  it  is  not 
this  carbon  that  we  want,  - it  is  the  sulfate,  and  that  dissolves  out 
readily.  The  data  obtained  proves  this.  The  objection  that  an 


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impure  barium  sulfate  is  obtained  was  verified  in  part  of  this  work. 
Grenerally  a white  barium  sulfate  is  obtained.  Once  in  a while,  a 
slightly  colored  precipitate  was  obtained,  but  no  more  often  than 
is  obtained  from  the  peroxide  bomb.  It  is  advisable  to  run  a check 
determination  on  the  reagents.  In  this  work,  checks  were  run  on 
most  of  the  work.  The  sulfur  content  of  the  chemicals  ran  about 
.0467  grams  of  barium  sulfate. 

Although  this  method  gives  good  results  for  low  sulfur  oils, 

it  is  rather  long  and  tedious,  taking  a little  longer  than  to  make 

four  combustions  with  the  peroxide  bomb.  Also  it  does  not  look 

very  much  like  a q_uantitative  determination  to  one  who  has  not  run 

them  before.  The  dish  after  ignition  is  covered  on  the  inside  even 
with  a 

upon  the  walls^carbon  material  and  a white  substance  so  that  one 
would  suspect  that  some  of  the  material  spattered  out  (when  as  a mat- 
ter of  fact  it  has  not,  at  least  6 or  7 determinations  have  been 
watched  closely  through  the  entire  ignition)  Another  place  that 
does  not  look  q[uantitative  is  when  the  evolution  of  fumes  takes 
place.  The  data,  however,  shows  good  checks  among  themselves  and 
with  the  peroxide  bomb  determination. 

2.-  IffiW  METHODS  TRIED 

Torossian*^^  in  October,  1921,  published  an  article  on  the  ac- 
tion of  anhydrous  stannic  chloride  on  oils.  Some  of  his  conclusions 
were  that: 

(a)Tin  tetrachloride  precipitates  tha  tarry,  resinous,  oxygena- 
ted, bituminous  bodies,  and  also  sulfur  containing  compounds  from 
crude  petroleum  and  its  crude  distillates,  by  forming  compounds  with 
them  and  also  by  polymerizing  action  upon  them.  (b)  The  tin  tetra- 
chloried  reaction  affords  a means  for  q^ualitative  and  q_uantit;ative 


" - ■ i 


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'if»v:J‘c>-r;jk.  tijp>.l.jU^*jt,  >4-f oil 

fc.-.  ao:£^-S  ^,'fQivh  To  <ti5x J^rrX^Vo ' 
b K't'  :5:1T  r .••,•4;{r.i^^  ^vm.i  60^^  •i-i^‘0fi'4'‘ 

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(14) 


tests  for  petroleum  products. 

Acting  on  these  statements,  a few  trials  were  made  to  separate 
the  sulfur  hearing  compounds  from  the  rest  of  the  oil  in  the  case 
of  cylinder  oil,  gasoline  and  fuel  oil.  If  these  statements  were 
true,  by  adding  stannic  chloride  to  an  oil,  the  sulfur  bearing  bod- 
ies would  be  precipitated  and  by  filtering  them  off  they  would  pos- 
sibly be  of  such  small  quantity  that  the  sulfur  bearing  bodies  from 
5 grams  of  oil  could  be  burned  in  a peroxide  bomb.  This  certainly 
would  be  a solution  to  the  determination  of  sulfur  in  oils  having 
a low  percentrage  of  sulfur.  But  several  difficulties  arose  before 
the  sulfur  compounds  got  to  the  bomb.  The  anhydrous  stannic 
chloride  precipitated  a blade  tar  from  the  cylinder  oil  and  a brown 
substance  from  the  gasoline,  but  separating  the  liquid  from  the 
tar  and  the  tar  from  the  glass  was  another  problem  and  the  writer 
was  unable  to  do  it.  Another  question  that  arose  was  whether  the 
sulfur  was  quantitatively  precipitated  or  not.  A letter  from 
I\ir.  Torossian  said  that  this  v;as  not  known  definitely  yet  because 
of  lack  of  data,  so  the  vnrk  along  this  line  was  not  continued. 

Selenium  oxychloride  was  tried  instead  of  the  stannic  chloride 
and  gave  the  same  results.  A tarry  precipitate  was  formed  which 
could  not  be  separated  from  the  glass  or  the  solution.  These  meth- 
ods bear  promise,  but  they  need  a great  deal  more  work  done  on  them 
before  any  definite  statement  as  to  their  quantitative  separation 
can  be  made. 

Another  method  suggested  itself  to  overcome  the  fact  that  a 
peroxide  bomb  would  not  burn  enough  oil.  That  was  the  use  of  a 
large  retort  bomb  having  about  nine  times  the  volume  of  the  peroxid€ 
bomb.  This  bomb  was  made  of  soft  steel  about  3 inches  in  diameter 


i ■,  — 


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r^fX^'.^'Ct-  ^•rtiV*q'i; 

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(15) 


and  E'a-  inches  deep.  The  to-p  which  was  clamped  on  had  two  small  holes 
in  it  about  3/8  inches  in  diameter  with  an  iron  pipe  about  8 

inches  long  leading  from  each  one.  By  calculation,  it  was  figured 
that  60  grams  of  sodium  peroxide  was  needed  to  burn  3 grams  of  oil. 
And  so  one  of  the  holes  in  the  top  of  the  bomb  was  closed,  5 scoop- 
fuls of  sodium  peroxide  and  3 grams  of  oil  placed  inside  and  thor- 
oughly mixed.  The  lid  was  clamped  on  tightly  and  the  bomb  placed 
over  a flame.  The  result  was  that  a flame  about  a foot  long  shot 
out  of  the  open  pipe.  On  opening  the  bomb  and  dissolving  out  the 
contents,  a great  deal  of  carbon  was  found,  - indicating  an  imcom- 
plete  combustion.  This  method  was  soon  given  up  because  it  was 
dangerous,  gave  an  incomplete  combustion,  and  required  too  much 
sodium  peroxide  which  would  contaminate  the  barium  sulfate  precipi- 
tate . 

Another  idea  resulted  from  the  possibility  of  the  loss  of  sul- 
fur in  the  ignition  of  the  oil  and  sodium  carbonate.  If  sulfur  diox- 
ide or  trioxide  was  given  off,  why  not  collect  them  in  a sodium 
carbonate  solution  and  thus  be  absolutely  sure  of  no  loss.  Difficul- 
ties arose  here  right  away  in  obtaining  a suitable  vessel  for  the 
combustion.  A pyrex  flask  was  tried  and  lasted  only  long  enough  to 
Show  the  impracticility  of  the  idea.  In  order  to  insure  good  com- 
bustion, air  or  oxygen  would  have  to  be  passed  into  the  flask.  vOien 
the  big  evolution  of  fumes  came  off,  the  absorbing  solutions  couldn'' 
take  care  of  them.  Several  bottles  of  water  or  a condenser  or  some 
kind  would  be  needed  to  condense  the  oil  fumes  before  entering  the 
sodium  carbonate  solutions.  This  would  make  a combustion  outfit  as 
tedious  and  hard  to  operate  as  the  combustion  tube,  so  it  was 


abandoned. 


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(16) 


3.-  V/OHK  ON  THE  ROTHE  METHOD 

The  method  used  to  start  with  was  changed  somevrhat  from  the 
original  Rothe  method  given  in  Holde's  '^Examination  of  Hydrocarbon 
Oils".  Prom  5 to  10  grams  of  oil  was  weighed  into  a liter  pyrex 
round  bottom  flash  containing  2 grams  of  magnesium  oxide.  Immedi- ■ 
ately  25  cc.  of  fuming  nitric  acid  was  added  (not  too  rapidly  because 
the  action  is  very  violent)  This  mixture  was  allowed  to  stand  in 
the  cold  until  the  reaction  had  nearly  ceased.  Then  it  was  heated 
very  slowly  on  a sand  bath  allowing  it  to  digest  from  -g-  to  1 hour. 
The  temperature  was  raised  until  the  nitrates  began  to  decompose. 
Then,  10  cc.  more  of  Aiming  nitric  acid  was  added,  allowed  to  act  and 
then  heated.  This  time  the  flash  was  heated  until  all  the  nitrates 
decomposed.  Finally  the  carbon  was  burned  off  the  flash  by  a 

burner.  The  residue  was  practically  white  and  on  being  tahen  into 

solution,  left  very  little  carbonaceous  material.  The  barium  sul- 
fate precipitate  was  pure. 

This  method  seemed  to  be  the  best  one  investigated,  so  more 
worh  was  done  to  try  to  out  down  the  time  element  and  increase  its 
dependableness.  On  adding  fuming  nitric  acid  the  second  time,  a 
very  violent  reaction  occurred,  even  glowing  and  bursting  into  a 
flame.  This  resulted  in  a loss  by  entrainment  of  the  lighter  par- 
ticles. So  concentrated  nitric  acid  (15  cc.)  was  tried  and  was 

found  to  give  very  satisfactory  results.  Then  the  question  arose 
as  to  whether  it  was  necessary  to  add  the  acid  the  second  time.  A 
few  experiments  showed  that  the  results  with  or  without  the  second 
addition  of  acid  were  practically  the  same  so  it  was  concluded  that 
it  was  not  necessary.  If  the  sulfur  is  not  oxidized  by  the  first 


I';  ^ ..  ’ 


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(17) 

addition  of  acid,  it  is  probat»ly  lost  before  the  second  amount  is 
added.  Furthermore  the  time  element  is  cut  down  considerably. 

The  next  problem  was  the  burning  off  ol  the  carbon  from  the  inside 
of  the  flask.  In  the  case  of  crude  oils,  lubricating  oils,  cylinder 
oils  and  fuel  oils,  quite  a large  deposit  of  carbon  was  left  on  the 
inside  of  the  flask.  This  carbon  had  to  be  burned  off  because  it 
would  form  an  oily  filtrate  and  thus  contaminate  the  barium  sulfate. 
To  bum  off  this  carbon,  the  flask  was  heated  on  a sand  bath  by 
the  full  power  of  an  adjustable  burner.  Then  another  burner  was 
used  to  burn  off  the  carbon  in  the  flask.  To  facilitate  the  burning, 
air  was  gently  blown  into  the  flask.  By  this  means,  the  carbon 
from  one  flask  could  be  burned  off  in  from  15  to  30  minutes.  But 
this  was  too  long  a time,  so  oxygen  was  tried  and  was  found  to  work 
satisfactorily,  cutting  the  time  element  in  half.  Oare  must  be 
taken  not  to  heat  the  flask  too  hot  or  the  white  material  will  fuse 
into  the  glass.  This  difficulty  is  avoided  if  the  flask  is  always 
heated  directly  over  a sand  bath  and  then  when  burning  off  the  car- 
bon with  a free  flame  to  be  careful  not  to  leave  the  flame  in  one 
place  long  enough  to  melt  the  glass.  The  carbon  burns  off  most 
readily  if  the  hot  part  of  the  Bunsen  flame  is  directed  about  3/8 
inch  behind  the  line  of  the  retreating  carbon. 

The  method  in  its  final  form  and  the  one  that  seems  to  be  the 
best  for  determining  sulfur  in  oil  where  the  percentage  is  low  is: 
Weigh  from  5 to  10  grams  of  oil  into  a liter  pyrex  flask  containing 
2 grams  of  magnesium  oxide.  Immediately,  add  carefully  25  oc.  of 
fuming  nitric  acid.  Allow  the  mixture  to  stand  until  the  reaction 
ceases.  Then  heat  gently  on  a sand  bath  for  about  3/4  of  an  hour; 
at  the  end  of  that  time,  gradually  raise  the  temperature  until  all 


v>?‘^' Ti^-t -Vc  fcr:i 

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JTf.  ■- ■ &>'  Cj'J’.  -dl  no'xl  'j^  8»£tp  :'i^^ 

f^o''  OiJ-  .'iJ^  tji#5  ^i;v;  r-'OH.^o  d» 

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II  i 


['*■'  ’ "Xf* 
I 


■tV.,  ^ ''^'J  • ' , ,j:yiy.Er  :W^^i  ' ViV^flfikir- 

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-’ .(T - ^ ^ ■ ^'■■- ' • ^ i 


(18) 

the  nitrates  are  decomposed.  Continue  heating  over  a full  Bunsen 
flame  for  several  minutes.  Blow  in  air  or  oxygen  and  heat  the 
flask  with  a free  flame  to  drive  off  the  carbon.  Cool  the  flask, 
moisten  the  white  residue  xvith  water,  add  concentrated  hydrochloric 
acid  and  heat.  Filter  off  the  carbon  and  precipitate  the  sulfur  as 
barium  sulfate  in  the  usual  manner. 

Some  objections  that  might  be  given  to  the  method  are:  (1) 

That  too  rapid  an  evolution  of  gas  comes  off,  - all  the  combustion 
and  digestion  must  be  done  under  a good  hood.  But  there  is  no  en- 
trainment of  particles  if  the  heating  is  not  too  rapid  and  the  data 
shows  no  loss  of  sulfur.  (2)  It  does  take  some  time  to  burn  the 
carbon  off  from  the  inside  of  the  flask.  (3)  A check  on  the  chemi- 
cals should  be  run,  A check  on  the  sulfur  content  of  chemicals  in 
this  work  was  run  with  nearly  every  set  of  determinations. 

Its  advantages  are  that  (l)  It  is  more  rapid  than  making  four 
combustions  with  the  peroxide  bomb  (2)  It  insures  a good  sized  bari-j 
um  sulfate  precipitate  because  several  grams  of  oil  can  be  taken. 

(3)  It  does  not  introduce  a lot  of  contaminating  salts  as  several 
combustions  with  the  peroxide  bomb  would.  (4)  The  method  is  consid- 
ered accurate  because  it  gave  good  checks  on  the  fifteen  oils  that 
were  run. 

It  was  thought  best  to  precipitate  the  sulfur  as  barium  sulfate 

because  the  volumetric  method'^^  with  sodium  thiocyanate  is  not  very 

accurate,  even  though  it  is  a bit  more  rapid.  In  determining  small 

percentages  of  sulfur,  it  is  better  to  sacrifice  the  small  amount  of 

time  gained  here  for  the  accuracy.  The  volumetric  titration  of 

benzidine  sulfate^^  with  standard  potassium  permanganate  was  not 

investigated.  The  gravimetric  determination  is  generally  more 
flr.mTrfl.tft  than  the  volumetric  any/vay. 


f'i  i ' f ‘U» 

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(19) 


III  RESULTS  Am)  DISGUSSIOR 


TABLE  I 

Wt.of  Fuel  Oil^ 

Wt.of  BaSO 

Wt.of  E3r 

fo3 

.5.2241 

.1254 

.2  gr 

.331 

5.1873 

.1292 

.2  gr 

.342 

5.1815 

.1345 

.2  gr 

.359 

5.1686 

.1255 

.3  gr 

.336 

5.0860 

.1188 

.3  gr 

.323 

5.1387 

.1252 

.5  gr 

.337 

5.0242 

.1292 

.5  gr 

.355 

5.0190 

.1290 

1.0  gr 

.356 

5.0541 

.1238 

1.0  gr 

.339 

Peroxide  Bomb  Check 

.367 

Wt.of  Fuel  Oil^^ 

5.6378 

.0905 

.01 

.222 

5.3397 

.0936 

.03 

.242 

5.9685 

.1031 

.20 

.240 

5.2475 

.1019 

.20 

.269 

Table  I gives  the  results  on  the  investigation  of  the 
best  amount  of  potassium  bromide  to  use.  Weights 
from  .01  gram  to  1.0  gram  of  KBr  v/ere  used  and  as  the 
data  shows  from  .2  to  .5  gram  is  enough. 


(20) 


TABLB  II 


Wt.Puel  Oil-Ill 

Wt.of  BaS04 

vVt . of  KBr 

Yol.Br2  Water 

io  s. 

5.2610 

.0780 

.2  gr 

0 

.162 

4.6938 

.0660 

.2  gr 

0 

.140 

5.6986 

.0875 

0 

1 cc 

.153 

This  table  shows  that  it  malces  very  little 
difference  whether  potassi-um  hromide  or 
bromine  water  is  used. 


TABLE  III 


Analyses  by  Method  of  Parr-Whittum 


Ho. 

' Kind  of  Oil 

Wt.  of  Oil 

' Wt.of  BaS04 

Percent  S. 

IV 

3. 7835 

.1257 

.458 

IV 

Fuel  Oil 

4.3886 

.1498 

.471 

Same  oil.  Four 

IV 

peroxide  bomb 
fusions. 

1.9608 

.0654 

.460 

VI 

Lubricating  Cffl 

5.5208 

.1377^ 

.344 

6.8628 

.1273^ 

.256 

VII 

n Tf 

5.7528 

.1117^ 

.268 

5.0117 

. 1424^ 

.39 

VIII 

1 

Fuel  Oil 

6.4988 

.1497^ 

.32 

6.7902 

.0877^ 

.179 

IX 

O sage  Crude 

8.1772 

.0972^ 

.164 

X 

BaS04  in  chemicals  already  subtracted. 

The  percentage  of  sulfur  by  the  method  of  Parr-Whittum  in  Tablelll 
proves  that  there  is  no  loss  by  sputtering.  If  there  ?/as  loss, 
the  results  would  not  checlc  so  well  for  the  reason  that  no  two 
determinations  would  sputter  out  the  same  amount. 


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^21) 


TABLE  IV 


Analyses  By  Modified  Rot he 


No. 

'Kind  of  Oil 

cn.  of  Oil  ’ 

Wt.of  3aS04 

Percent  3. 

Cylinder  Oil 

4.2145 

.0396 

.132 

X 

Blaclc 

7.0616 

.0854 

.167 

4.2108 

.1378 

.451 

VI 

® Lubricating 

5.1119 

.1801 

.486 

7.0007 

.1778 

.208 

VII 

^Lubricating 

6.5481 

.1545 

.327 

7.5836 

.2112 

.384 

VIII 

®Fuel  Oil 

5.2273 

.1512 

.395 

6.7233 

.1396 

.286 

IX 

®0  sage  Crude 

6.5613 

.1100 

.262 

9.0563 

1291 

.197 

XI 

OQus hi ng  Cmde 

6.5726 

.0896 

.189 

9.0935 

.1418 

.215 

7.6242 

.1002 

.181 

0 Vifax 

XII 

Distillate 

6.8975 

.0940 

.188 

6 . 0933 

.0891 

.202 

5.4571 

.0983 

.249 

XIII 

®Color  Oil 

6.6544 

.0838 

.175 

6.8970 

.1063 

.210 

HfV. 

[A 


f »• 
\ - 


F ^ 


,r 

I I 


i' 


I ■'  -.^ 


'-r.r- 


t^  ' '• 


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■ )•  ' 


« •¥” 


izz) 

TABLE  IV  (Cont . ) 


I'  Fo. 

' Kind  of  Oil 

' Wt.  of  Oil 

' 'Wt.  of  BaS04 

Percent  S. 

XIY 

^Finished  Wax 

4.4837 

0 

0 

6.0067 

0 

0 

5.0641 

0 

0 

8.0015 

.0510 

.088 

XV 

®Gas  Oil 

7.4657 

.0422 

.078 

5.9559 

.0185 

.042 

XV 

^Kerosene 

6.0147 

.0169 

.038 

6.0303 

.0175 

.040 

5.9521 

.0145 

.033 

XVII 

^Naptha 

5.8719 

.0143 

.033 

5.9682 

.0148 

.034 

^Gasoline 

5.4669 

.0160 

.041 

XVIII 

5.5376 

.0110 

.030 

6.2182 

.0582 

.12 

Crude  Pettole- 

XIX 

um,  Carlisle, 

6.1038 

.0436 

.09 

Illinois 

6.1900 

.0536 

.12 

9.0899 

.0977 

.14 

Kansas  Ciruie, 

XX 

Monte ornery 

6.7004 

.0798 

.16 

County 

6.5786 

.0734 

.15 

5.9942 

.0673 

.16 

Illinois  Crude 

XXI 

Montgomery 

5.1876 

.0723 

.19 

County 

5.5954 

.0876 

.21 

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(23) 


TABLE  Y 

Analysis  by  Modified  Rothe  Method 


No. 

Kind  of  Oil’ 

' Wt . 'of  Oil 

Ignition 

Perdent  Sul. 

5.9559 

2 

.042 

XVI 

Xerosene 

6.0147 

1 

.038 

6.0303 

1 

.040 

5.9521 

2 

.033 

XVII 

Naptha 

5.8719 

1 

.033 

5.9682 

1 

.034 

6.3212 

2 

.17 

6.3310 

2 

.20 

XX 

Xansas  Oil 

6 . 7004 

1 

.16 

6.5786 

1 

.15 

The  second  ignition  was  made  using  20  cc.  of  coneentrated 
nitric  acid.  In  the  single  ignition,  only  25  cc.  of  fum- 
ing nitric  acid  were  used. 


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(24) 

TABLE  VI 


Comparison  of  Three  Methods 


Fo. 

' Kind  of  Oil  ’ 

, Percent  Sul.  , 

' Percent  Sul.  ' 

' Percent  Sul. 

Rothe  Method 

Parr -Whit turn 

Peroxide  Bomb 

z 

‘ Cylinder 

.167 

.162 

.138 

.140 

.367 

.344 

VI 

® Lubricating 

.451 

.486 

.208 

.256 

VII 

® Lubricating 

.327 

.435 

.268 

.384 

.390 

.290 

Vill 

®Puel  Oil 

.395 

.445 

.320 

.390 

.214 

.179 

IX 

® Osage  Crude 

.286 

.262 

.164 

.042 

.037 

XVI 

® Kero  sene 

.038 

.040 

.249 

.31 

XIII 

® Co  lor  Cil 

.175 

.210 

.28 

.197 

.49 

XI 

®Cuslb.g  Crude 

.189 

.215 

.37 

lUinois  Crude 

.19 

.20 

XXI 

Montgomery 

.21 

County 

.16 

®Oils  received  from  Gosden  & Company,  Tulsa,  Oklahoma. 


tir'*- 


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(25) 

A oomparison  of  the  Peroxide  bomh  method,  the  modified  Rothe 
method  and  the  method  of  Parr  and  'nThittum  is  given  in  Table  YI. 

It  was  impossible  to  check  all  of  the  oils  by  all  of  the  methods  in 
the  time  available  so  only  the  oils  with  a fairly  high  percentage 
of  sulfur  (except  kerosene),  where  one  combustion  in  the  bomb  could 
be  made  were  used.  The  results  showing  the  comparison  of  the  modi- 
fied Rothe  method  and  the  Parr-¥hittum  method  show  that  the  Rothe 
method  gives  a little  higher  results  in  every  case.  In  none  of 
these  deteirminations  which  give  the  comparison  of  the  Modified 

Rothe  and  Parr-?^hittum  method  was  the  sulfur  in  the  chemicals  sub- 
tracted. This  should  make  no  difference,  since  there  is  as  much 
sulfur  in  the  chemicals  used  in  one  method  as  in  the  other  so  the 
subtractions  would  only  balance  each  other.  In  checking  the  Modi- 
fied Rothe  method  against  the  peroxide  bomb,  the  results  in  the 
case  of  the  fuel  oil,  kerosene  and  Illinois  crude  oil  were  practi- 
cally the  same,  checking  in  percentage  of  sulfur  in  each  case  to 
the  fourth  decimal  place.  The  color  oil  was  seven  in  the  fourth 
place  higher  in  the  case  of  the  peroxide  bomb,  and  two  in  the  third 
place  higher  in  the  case  of  Gushing  crude.  This  difference  is 
probably  due  to  experimental  errors  and  not  to  the  method. 


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(26) 

IV  SUMMARY  Am)  COITCLUSIOITS 

I.  Possible  methods  for  the  determination  of  sulfur  in  oils  have 
been  reviewed  and  the  three  most  promising  methods  investigated. 

II.  In  the  Parr-Whittum  method,  from  .2  to  .5  gram  of  potassium  bro- 
mide should  be  used. 

III.  It  malces  little  difference  whether  potassium  bromide  or  bromine 
water  is  used  as  an  aid  to  oxidation  in  the  Parr-Whittum  method. 
The  use  of  potassium  bromide,  ho?fever,  is  given  preference. 

IV.  About  25  cc.  of  fuming  nitric  acid  was  used  in  place  of  the 
5CD-40  cc.  of  concentrated  nitric  acid  as  used  in  the  original 
Rothe  method. 

V.  Two  grams  of  magnesium  oxide  instead  of  one  and  one  half  grams 
were  used  in  the  Modif  is;d  Rothe  method. 

VI.  It  is  not  necessary  to  burn  down  the  second  time  with  nitric 
acid  in  the  Modified  Rothe  method. 

VII.  Eighty  complete  determinations  and  as  many  more  incomplete  deter- 
minations of  sulfur  in  oils  have  been  run  besides  a great  deal  of 
speculative  work. 

7III.The  Rothe  method  as  modified  in  this  work  is  satisfactory  for  all 
the  oils  of  low^  percentage  sulfur  that  have  been  investigated. 

It  is  better  than  the  Parr-^Hiittum  method  because  , 

1.  It  is  quicker. 

2.  It  gives  a purer  BaSO^  precipitate. 

3.  There  is  no  loss  by  sputtering. 

4.  There  is  less  danger  of  absorbing  sulfur  from  the 
burner  flame. 

IX.  It  is  better  than  the  peroxide  bomb  method  because; 


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(27) 


1.  It  is  just  as  quiclc  if  three  or  four  combust  ions 
would  have  to  be  made. 

2.  It  permits  a larger  sample  of  oil  to  be  taken. 

3.  It  gives  an  accurately  weighable  quantity  of  BaS04. 

4.  It  does  not  require  any  special  apparatus. 


■ 


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f28) 

V BIBLIOaHAPHY 

1.  Bull.  Soc.  Ohem.  Paris,  Vol.21,  pp. 338-341. 

Min.  and  Soi.  Press,  Yol.81,  p.569. 

Ghem.  Zeit.,  Yol.E5,  IIo.E,  July  13,  1921. 

2.  Ghem.  and  Met . , Vol.25,  ITo.2,  1909,  p.440. 

3.  Zeitschr.  Angew.  Ghem.,  Vol.22,  1909,  p.440. 

4.  Ghem.  Zeit.,  Yol.26,  1902. 

5.  Ghem.  Zeit.,  Yol.21,  p.203. 

6.  Ber.  Yol.22,  p.3303. 

7.  Oh. Zeit.,  Yol.40,  p.476. 

8.  J.  See.  Ghem.Ind.,  Yol.l9,  p.508. 

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14.  Jour,  Anal,  and  Appl.  Ghem.,  Yol.6,  p.385. 

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18.  Jour. Soc.  Ghem.Ind.,  Yol. 18,  p.l056. 

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20.  Blair,  The  Ghemical  Analysis  of  Iron,  1906,  pp. 291-2. 

21.  Pranks,  Ohem. & Met.,  Yol. 25,  1^0.2,  July  13,  1921. 

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24.  Ghem.  Uews,  Yol.24,  p.  76. 


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25.  Gatterrjian,  Practical  Methods  of  Organic  Ghem. 

26.  Ghem.  Abs.,Vol.5,  1911,  p.l379. 

27.  Ghem.Zeit.,  Vol.7,  1893,  pp.99,  130. 

28.  Analyst,  Tol.l3,  pp. 43-45. 

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30.  Sanders,  Trans.  Ghem.  Soc.,  Vol.lOl,  1912. 

31.  Zeitschr.  Angew.  Ghem.,  Vol.22,  p.  440. 

32.  Jour.  Soc.  Ghem. Ind, Vol . 23,  p.562. 

33.  Petroleum,  Vol.7,  p.237. 

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35.  A.C.  Pieldner,  Ghemist,  Bureau  of  Mines. 

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38.  J.  Ind.  & Eng.  Ghem.,  Vol. 12,  pp. 482-485. 

39.  Parr-Whittum,  Unpublished. 

40.  Holde's  Examination  of  Hydrocarbon  Oils. 

41.  Rothe,  Vol. 20,  A.S.T.M.,  p.408. 

42.  Technical  Paper  26,  Bureau  of  Mines. 

43.  Unpublished  Thesis  at  U.  of  I. 

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45.  J.  Am.  Ghem.  Soc.  1903,  p.l215. 

46.  J.  Ind.  & Eng.  Ghem.,  Vol. 12,  pp. 171-2. 


